Evolution of Local Structural Ordering and Chemical Distribution upon Delithiation of a Rock Salt–Structured Li1.3Ta0.3Mn0.4O2 Cathode

Lithium‐rich disordered rock‐salt oxides have attracted great interest owing to their promising performance as Li‐ion battery cathodes. While experimental and theoretical efforts are critical in advancing this class of materials, a fundamental understanding of key property changes upon Li extraction is largely missing. In the present study, single‐crystal synthesis of a new disordered rock‐salt cathode material, Li_1.3Ta_0.3Mn_0.4O₂ (LTMO), and its use as a model compound to investigate Li concentration–driven evolution of local cationic ordering, charge compensation, and chemical distribution are reported. Through the combined use of 2D and 3D X‐ray nanotomography, it is shown that Li removal accompanied by oxygen oxidation is correlated with the development of morphological defects such as particle cracking. Chemical heterogeneity, quantified by subparticle level distribution of Mn valence state, is minimal during Mn redox, which drastically increases upon the formation of cracks during oxygen redox. Density functional theory and bond valence sum mismatch calculations reveal the presence of local short‐range ordering in the pristine oxide, which gradually disappears along with the extraction of Li. The study suggests that with cycling the transformation into true cation–disordered state can be expected, which likely impacts the voltage profile and obtainable energy density of the oxide cathodes.     

Capture of Organic Vapors Using Adsorption and Electrothermal Regeneration

Activated-carbon-fiber cloth (ACFC) is an alternative adsorbent to granular activated carbon (GAC) for removing and recovering organic vapors from gas streams. Electrothermal desorption (ED) of ACFC provides rapid regeneration while requiring less energy compared to traditional regeneration techniques used with GAC. This paper provides proof-of-concept results from a bench-scale ACFC adsorption system. The automated system captured 1,000 ppmv of hazardous air pollutants/volatile organic compounds (HAPs/VOCs) from air streams and demonstrated the use of ED, using ac voltage, to recover the HAP/VOC as a pure liquid. The desorbed HAP/VOC condensed onto the inner walls of the adsorber and was collected at the bottom of the vessel, without the use of ancillary cooling. Seventy percent of the HAP/VOC was collected per cycle as condensate, with the balance being retained in the regenerated adsorber or recycled to the second adsorber. ED with in-vessel condensation results in minimal N2 consumption and short regeneration cycle times allowing the process to be cost competitive with conventional GAC-based adsorption processes. This technology extends the application of carbon adsorption systems to situations that were previously economically and physically impractical.     

Electrical and optical properties of semi-insulating polycrystalline silicon thin films: the role of microstructure and doping

We have investigated the relationship between microstructure and electrical conductivity in semi-insulating polycrystalline silicon (SIPOS) with oxygen concentrations in the 2–35 at.% range and the effect of doping with boron, phosphorus, arsenic and erbium by ion implantation. SIPOS thin films are mixtures of silicon and silicon oxide phases. The chemical and morphological evolution of these phases upon annealing is emphasized. Electrical conductivity measurements are interpreted in terms of a physical model containing few free parameters related to the material microstructure. A direct extension of this model explains also the conductivity increase in SIPOS doped with elements of the third or the fifth group. In the last part of the paper, data of electroluminescence at 1.54 μm in Er-implanted SIPOS due to intra-4f transitions of the Er³⁺ ion are shown and discussed.     

Subreflector shaping to improve multiple-beam performance of a Cassegrain antenna

A method of designing multiple-beam antennas based on shaping the subreflector of an offset Cassegrain antenna is described. It is applied to a compact system having a diameter of 300? that is required to produce beams up to 4-6°either side of boresight. The performance is shown to be only slightly less than that obtainable by also shaping the main reflector, indicating that efficient multiple-satellite-access antennas can be designed without specially shaped main reflectors.     

Methodologies for the optimal design of parallel manipulators

In this paper the problem of determining a manipulator design so that its workspace corresponds to a prescribed workspace is considered. Two different strategies, resulting in two different types of optimization problem are considered. The first strategy attempts to obtain a good overall approximation to the prescribed workspace and results in an unconstrained optimization problem. The second strategy entails designing a manipulator so that its workspace fully encloses the prescribed workspace and results in a constrained optimization problem. Two specific formulations of the constrained problem are proposed. The first constrained problem simply aims to fit the manipulator workspace as exactly as possible to the prescribed workspace, while still ensuring that the prescribed workspace is fully enclosed. The second constrained optimization formulation is used to design a manipulator, the workspace of which fully encloses the prescribed workspace, but which is also well‐conditioned throughout the workspace with respect to some performance measure. The particular manipulator used to illustrate and evaluate these formulations is a simple 2‐dof planar parallel manipulator, and the final formulation is also applied to a 3‐dof planar parallel manipulator. Although the manipulators studied here are simple, the objective of this study is to obtain a robust numerical methodology which can be extended to more practical and complex manipulators. Copyright © 2003 John Wiley & Sons, Ltd.     

Stick-slip vibrations of a two degree-of-freedom geophysical fault model

This paper considers the behaviour of a two degree-of-freedom autonomous system with static and dynamic friction consisting of two blocks linked by springs on a moving belt. This system is the simplest model which has been used to simulate the dynamics of seismic faults. The friction force is assumed to be a decreasing function of the relative sliding velocity. The motion of the blocks is composed of a uniform stick motion, during which the divergence of the system is zero, and an accelerated slip motion, during which the divergence is positive. The mathematical model by definition concentrates the dissipation on the point where the slip motion ceases. It is assumed that slip occurs only in one direction. A three-dimensional Poincaré map and a scalar single variable map are discussed which characterize the dynamics of the system in a simple way. The one-dimensional map can be used to diagnose the chaotic behaviour of the full system, and quantities, similar to Lyapunov exponents, can be easily calculated which provide information regarding the system-sensitive dependence on initial conditions. The system dynamics illustrate the idea of studying the earthquake generation mechanism as a chaotic phenomenon.     

Silver electrodeposition from air and water-stable ionic liquid: An environmentally friendly alternative to cyanide baths

The influence of temperature on the kinetics and the morphology of silver deposits obtained from an air and water-stable ionic liquid (the 1-butyl-3-methyl imidazolium tetrafluoroborate) was studied by means of cyclic voltammetry and chronoamperometry. The nucleation and growth mechanisms have been investigated and the effect of temperature evaluated up to 200 °C. Dense, pure and very thin (about 0.3 μm) silver coatings, with decorative properties, have been obtained on commercial copper electrodes at different temperatures. The characterization of the deposits morphology has been performed by visual investigation and SEM microscopy. Data about thickness were acquired by Calotest® measurements. The deposits result constituted by pure silver as determined by combination of EDX microanalysis and Auger Electron Spectroscopy (AES). The deposition method promises to be a new, environmentally friendly, method for silver electrodeposition which is the reason for the absence of cyanide and volatile toxic solvents in the electroplating bath.     

Evaluating the solar resource: a review of problems resulting from temporal, spatial and angular variations

Accurate assessment of the availability of solar energy at the Earth's surface is hampered by difficulties associated with the variability of solar radiation in space and time and with the angular position in the sky hemisphere. This paper assesses each of these problem areas by highlighting the difficulties and the attempts to offset them. Major emphasis is placed on extrapolation and interpolation procedures, the sensitivity of inclined surfaces to variations in the solar input, numerical models for calculating the irradiance of inclined surfaces and the time scales for which these computations are valid.Finally, the reader is urged to consider the significance of these difficulties in light of both radiation measurement errors and the sensitivity of the application to imprecise determinations of the radiation environment.     

A recent assessment of cocoa and pesticides in Brazil: an unhealthy blend for plantation workers

Cocoa is the major source of income for the Brazilian state of Bahia and some 2.3 million people rely on the crop for their livelihood. Most cocoa is grown on large plantations where working conditions are often extremely poor. Few workers using pesticides on plantations, or on small-holdings, have had instruction about safe working practices. Protective clothing is rarely available. The result is frequent complaints about health. None of this likely to improve in the short term given Brazil's perilous economic situation.